Process for making olefin chlorohydrins



Feb, 24, 1948. c:.E. MORRELL Erm.. 2,435,591

PROCESS FOR KING OLEFIN CHLOROHYDRINS Filed Aug. 24, 1945 i 4 wl.- wmv-zn 1 Ms OQTLET Azo'nzor: 50 INLET 1 ,57 OLEFIN 'lrz'covny 2 Y Tawm l Ton/R 34 J0 C'cogsn gil `Tom/151m 27 um 35 Azza rn o rf me CHLonoHm/varlou Agusovs v TOWER 25 2 4 n IMU" Het. RECOVERY wwj w Tou/E2 3m IPP/NC M s f l rzmv NLE Patented Feb. 24, 1948 UNITED STATESk PATENT oI-'FICE` PROCESS FOR MAKING OLEFIN CHLOROHYDRINS Application August 24, 1945, Serial No. 612,458

The present invention relates to a method of making olen chlorohydrins from oleflns, and particularly to a method of making olefin chlorohydrins from olefms by a process wherein anhydrous HC1 is directly recovered as a valuable by-product.

Heretofore olefin chlorohydrins have been made by various methods; among which is one wherein hypochlorous acid is prepared separately from mercurio oxide and chlorine and is added to the olenic hydrocarbon with agitation and cooling and another wherein olen gases react with hypochlorous acid in the presence of excess steam and water at a temperature of about 100 C., but the most successful method has been one wherein chlorine is pre-dissolved in an aqueous medium and then the aqueous chlorine solution is owed 20 Claims. (Cl. 26o-634) the reaction is removedirom the reaction mixture in an HClrecovery tower by appropriate means such as stripping the reaction mixture with an lnert gas. The proportion by weight of HC1 to water in the hydrochloric acid removed by the stripping gas is greater than one to four, the composition of the HCl-H azeotrope at atmospheric pressure. Olen chlorohydrin is recovered in a chlorohydrin recovery tower by extraction or by means of a distillation which removes the chlorohydrin with some water. The distillation may be at atmospheric pressure or at reduced pressure or by concurrently with the olefin gas through an appropriate reaction vessel. When chlorine is dis-V solved in aqueous solution, presumably hypochlorous acid reacts with the olefin; the products of the reaction are olefin chlorohydrin, HC1 and some olen dichloride which is formed bv direct addition of chlorine to the olen. The HCI produced has heretofore been available as a byproduct only in the form of the dilute aqueous acid as it is obtained in the reaction or concentrated by distillation procedure, which gives a constant boiling aqueous solution of HC1 knownv action in sulfuric acid of suflicient strength, the

HC1 which is removed from the resulting solution by heating or by the action of a stripping gas has a higher ratio of HC1 to Water than that in the HC1-water azeotrope; it is then possible by simple fractionation to obtain anhydrous HC1 from this product.

The drawing is a iiowy diagram representing a preferred embodiment of the invention.

Stated broadly, the invention is practiced by contacting chlorine and olefin with aqueous sulfurie acid. This may be accomplished by contacting chlorine with aqueous sulfuric acid in one vessel followed bycontacting the solution with an oleiin in a second vessel or by contacting both chlorine and olen with aqueous sulfuric acid in a chlorohydrination tower. The HC1 formed by means of steam. If it is desired to concentrate the sulfuric acid, in the event that it is diluted in the removal of chlorohydrin, this is done by a distillation step in an acid concentrator, but the' acid may be reintroduced directly into the vessel wherein chlorine is introduced or into the chlorohydrination tower. The invention is practiced in a continuous manner as there is no substantial t rohydrination tower contains aqueous sulfuric acid when olen and chlorine are introduced.

Any unreacted olefine passes out of this tower through 8 and carries with it some HCl into the oleiin recovery tower 9 where the gases bubble through HC1 azeotrope, at a temperature substantiallyy below .its boiling point. which dissolves the HC1 present in the gases. Fresh azeotrope may be added at vIll and azeotrope containingi dissolved HCl may be withdrawn at II. The amount of HC1 removed from the chlorohydrination tower in the exit hydrocarbon stream will depend on the strength of the sulfuric acid used in this tower.` Thegas fromvwhich HCl has been removed leaves the olefin recovery tower 9 through line l2 and'may be reintroduced into line l through valve I3. A portion or all of this gas may be removed through I4 in orderto remove inert gases such as paraflins, etc., which may be present in the oleiin feed gas. The aqueous hsulfuric, reaction medium containing the products of the reaction is introduced through line l1 into the HC1 recovery tower A2l and the misremovcd chloric acid removed by the stripping gas is' greater than one to four. The stripping gas now containing HC1 leaves the tower through line 2l and enters tower 25 where it meets HCl-water aaeotrope which enters tower 26 through lines 4 peratureinthe ontowermaybe from the point of the solution to,50 C., buttheprel'erredrangeisfrom 0 to 39 C.

The olen chlorohydrin is recovered from the sulfuric acid solution by distillation means such as distillation vby the direct application of heat or by steam distillation.V These are preferably conducted under vacuum, especially when using Y sulfuric acid concentrations above about 40 to l2 and 35 at a temperature substantially below through 40 or returned by lines 39 and 43 for reuse in tower 2|. If i'eed gas was used as a stripping gas it can be returned to line I through line 31, valve 4| and line 38. The azeotrope containing dissolved HCi is removed from tower 26 through line 21 and passed through heater 28 and into tower 29 where heating means raises the temperature of the azeotrope which results in the dissolved HCl being expelled in a substantially anhydrous form through line 39 and condenser 3! to reflux drum 32 from which reflux is returned to tower 29 through valve 62 and line 34. The anhydrous HC1 is passed out of the system through line 33. The azeotrope which has been freed 1n tower 29 from dissolved HC1 is recycled to tower 26 through line 35 and cooler 36. The reaction mixture, substantially reduced in HCl content, is introduced into the chlorohydrin recovery tower 45 through line 44 and in this tower olefin chlorohydrin is removed through line 48 by a. distillation process, which is preferably conducted under vacuum. Steam may be introduced into tower 45 through line 46 where it is found desirable to remove the oleiln chlorohydrin by steam distillation. The aqueous sulfuric acid from which olefin chlorohydrin has been removed is withdrawn from tower 45 through line 4l and if its strength is such that lt can be used again in the chlorohydrination tower 1, it is then introduced into that tower by passing through valve 49, line G3, valve 81 and line 1I: but if it is desirableto concentrate the sulfuric acid, thlsis done in the acid concentration tower 5l into which it is introduced by passing through valve 49 and line 50, water vapor being withdrawn through line 55. The acid which has been concentrated to the desired strength is then introduced into the chlorohydrination tower. 1 by passing bthrough line 59, valve 61 and line 1l.

Aqueous sulfuric acid having 2li-80% by weight of sulfuric acid may be used in the chlorohydrination tower. The proportion of olefin to chlorine in the chlorohydrination tower is adjusted such that there is never an excess of chlorine over the amount required to react with the olen present, according to the follow- 50 wt. percent, in order to avoid decomposition of the chlorohydrin. The olefin chlorohydrin may also be .recovered by extraction of the sulfuric acid solution with selective solvents such as aliphatic ethers such as diethyl ether and diisopropyl ether.

It is possible that small amounts of HC1 may be present in the sulfuric acid that is returned to the chlorohydrination tower because it may not be feasible to remove all of the HCl in the steps preceding. The HCl concentration in the reaction liquid in the chlorohydrination tower should be kept below about one mole per liter to suppress the formation of olefin dichloride. The concentration of olefin chlorohydrin is also pre1- erably kept below about 1.0 to 1.5 moles per liter in order to suppress the oxidative action of chlorine on the olefin chlorohydrin.

Although the drawing represents one flow system according to which the invention may be practiced, the practice of the invention is not to be restricted to that system but it may. be practiced successfully in other systems, such as one in which an initial charge of dilute sulfuric acid is alternately contacted with chlorine and olen in separate towers and wherein the sulfuric acid is rst contacted with chlorine, the sufuric acid containing dissolved chlorine then being carried to a second contacting tower where it is contacted with oleiin and wherein the said olen iiows countercurrently or concurrently with the said sulfuric acid solution containing dissolved chlorine.

It is important that when a gas such as chlorine or a gaseous olefin is introduced into *he liquid phase that the gas be finely dispersed and this can be accomplished in a number of ways, one preferred being to pass the gas through a porous alundum disk.

The following examples represent some applications of this process to the manufacture of propylene chlorobydrin. It ls not intended, however, that the process be restricted to 'the manufacture of propylene chlorohydrin but these examples are given to show specific embodiments of the invention by way of illustration.

Example 1 An initial charge of 65 wt. per cent HzSO4 was contacted with nely dispersed chlorine in a contacting tower wherein the chlorine flowed countercurrent`y to the sulfuric acid. The sulfuric acid solution containing dissolved chlorine was then conveyed into a second tower where a finely dispersed stream of propylene, in excess of a mola] proportion to the dissolved chlorine, was introduced and in this tower the propylene flowed concurrently with the liquid. The initial charge was continuously recirculated through the two towers until a chlorohydrin concentration of one mole/liter had'been reached. The temperature of the circulating acid was maintained at 1011 C. Anhydrous HC1 can be recovered from unreacted propylene by .passing the gases into HCl-azeotrope, and then distilling off anhydrous HC1 from .this enriched solvent. Additional HCl tempts to distiu the chlorohydrin directly from the reaction mixture at atmospheric pressure, without dilution or the use of a stripping gas, resulted in such extensive reaction of the acid and chlorohydrin that only decomposition products were distilled, and the acid solution rapidly 4became black.

Example 2 An initial charge of HzSO4 .(25% by wt.) was contacted at a temperature of 10-11" C. with finely dispersed chlorine fed at a rate to'nearly saturate the solution. The HzSOq. solution containing dissolved chlorine was fed into the bottom of a second tower where propylene was introduced in a nely ydivided state and in amount in excess sof that required to react with all of the chlorine dissolved in the solution. The solution was recirculated between the towers until it acquired a concentration of olefin chlorohydrin of one mole/liter. Under these conditions 95 mole per cent of the chlorine' was consumed in the chlorohydrination reaction and only 5% was consumed in an addition reaction to produce propylene dichloride. The chlorohydrin was separated from this reaction mixture without decomposition by a single distillation at atmospheric pressure.

While the present invention'has been described in the above examples with specific reference to propylene, it also applies to the preparation of chlorohydrins from other oleilns, both gaseous and liquid. In working with olefins, which are more reactive with sulfuric acid, it is 'desirable to use sulfuric acid of sufliciently low strength to avoid substantial hydration or sulfation of the olefin at the reaction temperature of the chlorohydrination. For example, with oleflns such as ethylene, propylene and the n-butenes sulfuric acid concentrations up to about 80% may be used, while with tertiary olefins such as isobutylene,

the sulfuric acid concentration should be preferablv below about 50%.

What is claimed is:

1. An improved process for making olefin chlorohydrins/which comprises reacting chlorine with an olefin in the presence of a 20-80% by weight aqueous solution of sulfuric acid, separating HCl from the reaction mixture and then separating the olefin chlorohydrin at a temperature below its decomposition temperature.

2. An improved continuous process for making olen chlorohydrins which comprises continually passing chlorine and an olefin into a 20-80% by weight aqueous solution of sulfuric acid, continuously removing the reaction mixture from the reaction zone, separating HC1 from the reaction mixture, separating the olen chlorohydrin at a temperature below its decomposition temperature and continually returning the aqueous sulfuric acid to the reaction zone. I

2i An improved process for making olefin chlorohydrins which .comprises passing olen and chlorine separately into a 20-80% by weight aqueous solution of sulfuric acid at a temperature of from the freezing point of the reaction mixture to 50 C., separating HC1 from the reaction mixture and then separating the olefin chlorohydrin at a temperature below its decomposition temperature.

4. Process according to claim 3 in which the olefin is propylene.'

5. Process according to claim 3 in which the reaction temperature is 10 C.

-6. Process according to claim 3 in which the strength of the sulfuric acid is .65% by weight.

7. Improved process for making oleflnchlorohydrins which comprises passing `gaseous chlorine and olefin separately into a 20-80% by weight aqueous solution of H2SO4 at a temperature of from the freezing point of the solution to 50. C. in a 'chlorohydrination tower, removing part of the HCl formed in the said chlorohydrination tower in an HC1 recovery tower by passing through the solution a stripping gas, removing the oleiin chlorohydrin in a chlorohydrin recovery tower by passing steam through the solution, concentrating the H2504 to a degree that the per cent by Weight of H2SO4 is from 20-80%, and recycling the concentrated H2804 into the chlorohydrins.- tlon tower. v

8. Process according to claim 7 in which the olen is propylene.

9. Process according to claim 7 in which the reaction temperature is 10 C.

10. Process according to claim .7 in which the initial concentration of sulfuric acid is 65% by weight-and in which the concentration of the recycled sulfuric acid is 65 by weight.

ll'. An improved process for making oleiinv chlorohydrins which comprises reacting chlorine with an olefin in the presence of a 2080% by Weight aqueous solution of sulfuric acid, separating aqueousnHCl having a proportion by weight of HC1 to water greater than one to four from the reaction mixture and then separating the olefin-chlorohydrin at a temperature below its decomposition temperature.

12. An improved continuous process for making olefin chlorohydrins which comprises continually passing chlorine and an olen into a 2080% by weight aqueous solution of sulfuric acid, continuously removing the reaction mixture from the reaction zone, separating aqueous HC1 having a proportion by weight of .HC1 to water greater than one to four from the reaction mixture, distilling 0E the olefin chlorohydrin below its decomposition temperature and continually returning the aqueous sulfuric acid to the reaction zone.

13. Improved process for the manufacture, of olen chlorohydrins comprising passing chlorine into dilute sulfuric acid in a first vessel until the solution is saturated with chlorine, introducing the dilute sulfuric acid solution saturated with chlorine into a second vessel, reacting the solution in the second vessel with gaseous olefin, maintaining the `temperature in the second vessel between the freezing point of the solution and 50 C., separating anhydrous HC1 from the reaction mixture and then distilling oil the olefin ly into a 2080% by weight aqueous solution of sulfuric acid gaseous olefin and gaseous chlorine at a reaction temperature offrom the freezing .point of the solution to 50 C. in a chlorohydrln- 15. Process according tc claim 14 in which' the anhydrous hydrochloric acid is removed at the hydrochloric acid recovery zone by passing through the said zone an inert stripping gas,

16. Process according to claim 14 in which the 8 sulfuric acid gaseous olefin and gaseous chlorine at a reaction temperature of from the freezing point of the solution to 50 C. in a chlorohy- .drination zone and maintaining the proportion of olefin to chlorine such that there is always an excess of olen over thatrequired to react with all of the chlorine, whereby some of the hydrochloric acid formed by the reaction is carried out of the chlorohydrination zone by the excess olens and recovering it as anhydrous HC1, introducing the reaction mixture into a hydrochloric acid recovery zone, passing through this zone inert 'stripping gas whereby the hydrochloric acid concentration of the dilute sulfuric acid from tion zone and maintaining the proportion of olen to chlorine such that there is always an excess of olein over that required to react with all of the chlorine, whereby some of the hydrochloric acid formed by the reaction is carried out of the chlorohydrination zone by the excess oleiins and recovering it as anhydrous HC1, introducing the reaction mixture in to a hydrochloric acid recovery zone, passing through this zone inert stripping gas whereby the hydrochloric acid is substantially all removed from the solution as,

HCl mixed with stripping gas, recovering anhydrous HC1 from the stripping gas, introducing the olen chlorohydrin-sulfuric acid solution substantially reduced in hydrochloric acid into an olen chlorohydrin recovery zone, passing steam through the oien chlorohydrin recovery zone whereby the olefin chlorohydrin is removedand the sulfuric acid is diluted, introducing the dilute sulfuric acid into an acid concentrating zone, concentrating the sulfuric acid by distillation of the water until the concentration of sulfuric acidv is 20-80% by weight and introducing this acid into the chlorohydrination zone. Y

18. Improved process for the manufacture of olen chlorhydrins comprising passing separately into a 20-80% by weight aqueous solution of is substantially all removed from the solution as HCl having a proportion by weight of HC1 to water greater than one to four mixed with stripping gas, contacting the aqueous hydrochloric acid mixed with stripping gas with HCl-water azeotrope in a separate zone, whereby the HC1 is dissolved in the azeotrope, introducing the azeotrope containing dissolved HC1 into another zone and applying heat whereby the dissolved HC1 is removed as substantially anhydrous HC1, introf ducing the oleiin chlorohydrin-suliuric acid solution substantially reduced in hydrochloric acid into an olen chlorohydrin recovery zone, passing steam through the olefin `chlorohydrin recovery zonewhereby the oleiln chlorohydrin is removed and the sulfuric acid is diluted, introducingthe dilute sulfuric acid into an acid concentration zone, concentrating the sulfuric acid by distillation of the water until the concentration of sulfuric acid is 20-80% by weight and introducing' this acid into the chlorohydrination zone.

19. Process according to claim l' in which the Ainert stripping gas ls methane.

the inert stripping gas is steam. l

CHARLES E. MORRELL. JAMES K. SMALL. y HOWARD L. .YOWELL REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 2,107,789 Harford Feb. 8, 1938 2,378,104 Reed 7......- June l2, 1945 2o. Process. according tc claim 1'? in which' 

